Manufacture of new secondary disazo dyes and their application



' Patented May 6, 1930 UNITED STATES PATENT OFFICE I JAMES BADDILEY, F BLACKDEY, MANCHESTER, ENGLAND, ASSIGNOR T0 BRITISH DYESTUFFS CORPORATION LIMITED, 01'' BLACKLEY, MANCHESTER, ENGLAND MANUFACTURE 01'' NEW SECONDARY DISAZO DYES AND THEIR APPLICATION No Drawing. Application filed Kay 3, 1929, Serial No. 360,314, and in Great Britain December 18, 1926.

.In my copending application Serial No. 193,388 I have described a process for dyeing regenerated cellulose material directly with the secondary disazo dyestufis obtained by 5 combining the diazo' compound obtained from a nitroaniline or a homologue or derivative thereof not containing a sulphonic or carboxylic acid group with any middle component, rediazotlzing and combining with a periaminonaphthol sulphonic acid, including the N-substitution product of the latter in this term.

I The present invention relates to a process for d eing regenerated cellulose material with t e d es referred to above, consisting in reducin t e nitro group of the dyestuffs so obtaine with a suitable agent, for example,

sodium sulphide, the reduced dyestuiis being usingior dyeing. These reduced dyestufis may be represented by the general formula wherein R represents a divalent benzene residue free from sulphonic or carboxylic groups, R represents a divalent benzene or naphthalene residue and R represents a coupled 1:8-aminonaphthol sulphonic acid.

I have found that the new dyestufli's generally possess the property of dyeing regenerated cellulose rayons such as viscose rayons,

amino-para-cr'esol methyl ether at about 10 49 O. by stirring overnight. The mixture is then heated to about 30 C. and rediazotized by addition of a further amount of hydrochloric acid and 69 parts of sodium nitrite, the mixture throughout being acid to Congo red. When diazotization is complete, the diazo suspension is cooled with ice and added gradually to, an ice-cold alkaline solution of 319 arts of 1 8-aminonaphthol-3 fi disulphonic acid containing sufiicient caustic soda to or sodium carbonate to maintain the mixture alkaline throughout the coupling. When combination is complete about-360 parts of sodium sulphide crystals are added and the mixture stirred overnight at room tempera- 5E ture, during which time the nitro group is completely reduced. The mixture is then heated up, made neutral to litmus by addition of hydrochloric acid and the dyestuif isolated by addition of common salt, filtered 0 off and dried. It dyes viscose rayon a level greenish-black shade.

, The dyestuifs obtained by this invention may be applied to fabrics of cotton or of regenerated artificial silks in the usual way. 05 For example a dyebath maybe made up from 6 parts of the dyestuiiof one of the examples below and 3,000 parts oi water. 100 parts of viscose silk are entered into the bath which is then heated to the boil. 30 parts of Grlaubers salt or common salt are then added and the dyeing continued for hour at or near the boil. Soap may be added to the dyebath if desired. The viscose silk is dyed a full black shade, which may be modified by diazotization on the fibre and development with, say, m-toluylenediamine, whereby the fastness to washing and to acids is increased.

' p-nitroanlline p-nltroa'uillne Examples of dyes to which my invention is belipplicable are quoted in the following ta e:

lulose materials in even level shades which comprises applying to said regenerated cellulose material the secondary disazo dyes Secondary disazo colours from Shade on viscose silk oi the prod- First component Middle component 'ucts reduced with sodium sul- End component (coupled alkaline) Y scribed p-xylidine p-nltroanlline D m-toluldine p-nitroanlliue p-nltroaniline m-nltroanlllne o-ehloro-p-p-nitroanlllne D0. P m-nitro-p-toluldlne Maltre-o-anisidinev naphthylamiue Do. Do.

meta-amiuo-p-cresol, methyl ether metalsamino para-cresol methyl ether Do.

l-napihthylamine-fi and 7 sulphoulc meta-amino-para-cresol methyl ether Brownish-black Brownish-black Olive-black Black Olive-black Brownish-black Greenish-black Grey-black Black 1:8 agiiuonaphthol l-acetylamino-8 -naphthol 3:6.-d i s u lphonic acid 1:8 a1ninonaphthol 2:; disulphonic acid 1:8 aminonaphthol 3:6 disulphonic acid Do. 1:S-aminonaphtholl-sulphonic acid 1:8 aminonaphthol 3:6 disulphonic acid . Black Dull blue Do. 1:S-amino-naphthol-4-sulphonic acid Greenish-black 1:8 aminonaphthol 3:6 disulphonic acid What I claim and desire to secure by Let ters Patent is 1. The process of dyeing regenerated cellulose material in level shades which comprises immersing the material in a bath containing a dye obtained by coupling a diazotized amine having the formula whereinR represents a divalent benzene residue free from sulphonic and carboxylic groups with a middle component, having theformula R NH wherein R represents a phen l or naphthyl residue, rediazotizing, coup ing with a sulphonated periaminonaphthol in alkaline solution,- and reducing the nitro group.

2. Regenerated cellulose material dyed with dyes obtained by coupling a diazotized amine having the formula O N-R NH wherein R represents a divalent benzene residue free from sulphonic and carboxylic groups, with a middle component having the formula R NH wherein R represents a' phenyl or. naphthyl residue, rediazotizing, coupling with a sulphonated periamino naphthol in alkaline solution and reducing the nitro group.

3. The process of dyeing regenerated cellulose materials in even level shades which comprises applying'to said regenerated cellulose material the secondary disazo dyes having the general formula whereinR represents a divalent benzene residue free from sulphonic or carboxylic groups, R represents a divalent benzene-or naphthalene residue and R represents a coupled 1 :S-aminonaphthol sulphonic acid.

4.'The process of dyeing regenerated cel- 3 having the general formula wherein R represents a I divalent benzene residue free from sulphonic or carboxylic groups, R represents a divalent benzene or naphthalene residue and R represents a coupled 1:8-aminonaphthol sulphonic acid and in which the H N group is attached to the R in the para position to the azo group.

5. The process of dyeing regenerated cel-' lulose materials in even lelyel shades which comprises applying to said regenerated cellulose material the secondary disazo 'dyes having thegeneral formula wherein R represents a divalent benzene or naphthalene residue and R represents a cou pled 1:8-amin0naphthol sulphonic acid.

. 7.- The process of dyeing regeneratedcellulose materials .in even level shades which comprises applying to said regenerated cellulose material the secondary disazo dyes having the general formula phide as de-' lulose material the secondary disazo wherein R represents a divalent alkyl substituted benzene residue and R represents a coupled 1 :S-aminonaphthol sulphonic acid.

8. The process of dyeing regenerated cellulose materials in even level shades which comprises applying to said regenerateddceh .3

having the general formula wherein R represents a divalent benzene residue free from sulphonic or carboxylic groups and R represents a coupled 1 :8-aminonaphthol sulphonic acid and in which the H N group is attached to the R in the para position to the azo group.

'9. The process of dyeing regenerated cellulose materials in even, level shades which comprises applying to said regenerated cellulose materials the secondary disazo dyes having the general formula OH: M MQM...

\ cm I wherein R represents a coupled 1:8-aminonaphthol sulphonic acid. v

10. The process of dying regenerated cellulose materials in even, level shades which comprises applying to said regenerated cellulose inaterial the secondary disazo dyes having the probable formula a on NBz v W WZ QNWM EBA 0:11

11. Regenerated cellulose materials dyed with the secondary disazo dyes having the general formula wherein R represents a divalent benzene residue freefrom sulphonic or carboxylic groups, R represents a divalent benzene or naphthalene residue and R represents a coupled 1:8-aminonaphthol sulphonic acid,

the said regenerated cellulose material having an even, level shade.

12. Regenerated cellulose materials dyed with the secondary disazo dyes having the general formula wherein R represents a divalent benzene residue free from sulphomc or carboxylic groups,

. R 'represents a divalent benzene or naphthalene residue and R represents a coupled 15 8- aminonaphthol sulphonic acid and in WhlCh the H N group is attached to the R in the para position to the azo roup, the said regenerated cellulose material having an even,

. level shade.

13. Regenerat'ed cellulose materials dyed with the secondary disazo dyes havingthe general formula wherein R represents a divalent benzene risidue or the chloro, alkyl or alkoxy derivatives of such residue, the said residue represented by B, being free from sulphonic or carboxylic groups,'R represents a divalent benzene or naphthalene residue and R represents a coupled 1 S-aminonaphthol sulphonic acid and in which the H N group is attached to the R in the para position to the azo group, the said regenerated cellulose material having an even, level shade.

14. Regenerated cellulose materials dyed with the secondary disazo dyes having the general formula n wherein R represents a divalent benzene or naphthalene residue and R represents a coupled 1:8-aminonaphthol sulphonic acid, the said regenerated cellulose materials having an even level shade.

15. Regenerated cellulose materials dyed with the secondary disazo dyes having the general formula wherein lit represents a divalent alkyl substituted benzeneresidue and R represents a coupled 1: S-aminonaphthol sulphonic acid, the said regenerated cellulose materials having an even levelshade. I

16. Regenerated cellulose materials dyed with the secondary disazo dyes having the general formula llil naphthol sulphonic acid, the'said regenerated wherein R represents a coupled 1 S-aminocellulose materials having-an even level shade. 18. Regenerated cellulose materials dyed with the secondary. disazo dyes having the general formula on NB: 'om

I on, no. 0.3

the said regenerated cellulose materials having an even level shade.

In witness whereof I aflix my signature.

JAMES BADDILEY. 

